Perfumery compositions

ABSTRACT

W-HYDROXYMETHYL LONGIFOLENE AND/OR W-ACYLOXYMETHYL LONGIFOLENE WHEREIN THE ACYL GROUP HAS FROM 2 TO 4 CARBON ATOMS, PREFERABLY 2, MAY BE USED TO ADVANTAGE IN PERFUMERY COMPOSITIONS AS FIXATIVES, BLENDING AND ENHANCING AGENTS.

nited States Patent 3,745,131 PERFUMERY COMPOSITIONS Anthony J. Curtis, Southsea, John F. Janes, Epping, Essex,

and Brian G. Jaggers, Romford, Essex, England, as-

signors to Bush Boake Allen Limited, London, England No Drawing. Filed Mar. 19, 1969, Ser. No. 808,665 Claims priority, application Great Britain, Mar. 21, 1968,

13,756/68; June 28, 1968, 31,033/68 Int. Cl. Cllb 9/00 U.S. Cl. 252-522 21 Claims ABSTRACT OF THE DISCLOSURE w-Hydroxymethyl longifolene and/or w-acyloxymethyl longifolenes wherein the acyl group has from 2 to 4 carbon atoms, preferably 2, may be used to advantage in perfumery compositions as fixatives, blending and enhancing agents.

This invention relates to perfumery compositions of the type Where a number of odoriferous materials, of synthetic or natural origin, are admixed to fonm a compounded perfumery concentrate.

Such concentrates may find use as such or after dilution, but more usually they are added in small proportions to other materials, such as to space sprays or to soap, detergent, cosmetic or deodorant compositions, or to substrates such as talc, fabrics, fibres or paper products, in order to provide them with agreeable olfactory properties. Thus such concentrates (as well as the aforesaid perfumed materials) are products of commerce and the perfumery concentrates may comprise a simple or complex mixture of individual perfumery compounds.

It is known that the sesquiterpene longifolene is obtained as a by-product in the refining of Indian oil of turpentine. It may also be obtained from other pine extracts. It has the structure (I). It has been proposed by Nagai et a1. (Chemical Abstracts 56, 1295 if (1962)) and by Nayak, Santhanakrishnan and Sukh Dev (Tetrahedron, 19, 2281-2292 (1963)) to react longifolene with formaldehyde in the presence of acetic acid according to the Prins reaction and thereby prepare 'w-acetoxymethyl longifolene (II) and therefrom w-hydroxymethyl longifolene (III). These authors do not, however, suggest that these compounds are other than chemical curiosities without commercial value.

CH-CHzOH longifolene w-acetoxymethyl w-hydroxymethyl longifolene longifolene (II) (III) We have now found that w-hydroxymethyl longifolene (III) and the lower w-acyloxymethyl longifolene derivatives, such as w-acetoxymethyl longifolene (II) are valuable ingredients of compounded perfumery concentrates and materials perfumed therewith. Firstly this is because in such concentrates and perfumed materials these compounds have the most surprising effect that this incorporation in some way makes the basic note of the perfume last longer, that is the compounds appear to have some fixative effect on the other more volatile perfumery ingredients of the composition and such other ingredients appear to be lost less rapidly from the composition. Secondly, these longifolene derivatives have the effect of blending together the individual oduors of the of the other perfumery ingredients of the composition resulting in the composition as a whole having a more harmonious perfume note and therefore a more im- "ice mediate impact on the connoisseur without the need to allow the composition to mature. This is an effect which we have not hitherto noted among perfumery chemicals. Thirdly, the presence of the longifolene derivative in some way enhances the top note quality of the composition causing the top note produced by some other ingredient to be more dominant in the overall composition.

Accordingly, the present invention provides a compounded perfumery composition which comprises an admixture of perfumery compounds including w-hydroxymethyl longifolene and/or an w-acyloxymethyl longifolene wherein the acyl group has from 2 to 4 carbon atoms.

These longifolene derivatives may be made by the process previously described or by other modifications of the Prins reaction. One particularly good method involves heating longifolene with a slight molar excess of paraformaldehyde in glacial acetic acid as solvent. A little of a strong protonising agent, such as sulphuric acid, zinc chloride or boron trifiuoride, may conveniently be added as catalyst. After removal of some of the excess acetic acid by distillation, the w-acetoxymethyl longifolene product may be isolated and purified by treatment with water to remove the remainder of the acid followed by extraction with a suitable solvent before final purifiaction by fractional distillation under vacuum. The w-hydroxymethyl longifolene may be made from the acetoxy derivative by hydrolysis with an alkali, particularly with potassium hydroxide in an aqueous ethanol solvent. It may be obtained as a solid by crystallisation from light petroleum. If desired some other acyloxymethyllongifolene derivatives may be made instead of the acetoxy derivative by use of the appropriate acid instead of acetic acid and the hydroxymethyl compound prepared therefrom by similar saponification.

The propionoxy-, butyroxyand iso-butyroxy-methyl longifolene derivatives have not hitherto been described and as new chemical compounds accordingly constitute a further aspect of the present invention.

Accordingly, the invention also provides longifolene derivatives of the general formula 5 on-cmocon where R is an alkyl group having two or three carbon atoms.

The w-hydroxymethyl longifolene and the abovedescribed acyl derivatives thereof have been found to be useful fixatives for a wide variety of common perfumery compounds in that in some way unknown they retard the loss thereof by volatilisation. This effect appears to be particularly marked in conjunction with Patchouli oil and with Vetivertype perfumery compounds, e.g. with Vetiveryl acetate, Vetiver oil, Cedar wood oil and, especially, Sandalwood oil. It is also manifested with ionone and/ or methylionone compounds and'with perfumery lactones,

particularly with 'y-nonalactone as well as with citronellyl esters, geraniol and phenyl ethyl alcohol.

Moreover, it has been found that when the w-hydroxymethyl longifolens or an acyl derivative thereof is used in association with a perfumery aldehyde, a more pronounced perfumery effect is obtained with the n-alkanals and methyl-n-alkanals having from 7 to 12 atoms; the effect with methyl nonyl acetadehyde is particularly noteworthy.

In use for the aforesaid purposes, the aforesaid longi- I folene derivatives will normally comprise from 0.1 to 10%, or even up to 20% by weight based on the total weight of perfumery ingredients in the compounded perfumery concentrate, but they are preferably employed in 37% of the concentrate on this basis. Moreover, the invention envisages the sale of a blend of an w-acyloxymethyl longifolene as specified with w-hydroxymethyl longifolene and/or with at least one other compound useful as an odoriferous ingredient of a compounded perfumery concentrate for use in the preparation of a more complex perfumery concentrate or perfumed material. The longifolene derivative(s) will normally comprise at least 50% by weight of such blends.

The compounded perfumery concentrates of the invention find use in a wide variety of perfumed materials. For example, the concentrates may find particular use in the formulation of coutourier-type perfumes, cologne or toilet waters, space sprays or they can be blended in soap, detergent or deodorant compositions including bath salts, shampoos, or in cosmetic preparations, such as face creams, talcum powders, body lotions, sun cream preparations and in male toilet products such as shave lotions and creams. The compositions can also be used to perfume substrates such as talc, fibres, fabric and paper products.

The following two preparations illustrate the production of the longifolene derivatives for use in the compounded perfumery concentrates of the invention, illustrative of which are those formulations set out in Examples 1-3.

PREPARATION I w-Acetoxy-methyl longifolene Longifolene (1,020 g.) and acetic acid (2,000 ml.) were placed with para-formaldehyde (365 g.) in a 5 litre flask and the mixture was refluxed at 110 C. for 20 hours. Excess acetic acid was distilled off and the crude acetate mixture washed with water (500 ml.), twice with a solution of sodium bicarbonate (500 ml.) and once with water (500 ml.). The resulting oil was dried over anhydrous sodium sulphate and distilled under reduced pressure to give the desired compound (about 500 g.) which could be purified by further distillation.

The novel compounds of the invention may be made by an analogous procedure employing in place of acetic acid, the appropriate propionic or butyric acid.

PREPARATION II w-Hydroxy-methyl longifolene Potassium hydroxide (168 g.) was dissolved in water (168 g.) and methyl alcohol (1,000 ml.). Approx. 350 grns. of the crude distilled w-acetoxymethyl longifolene obtained as in Preparation I was slowly added to the cold alkali solution and the mixture allowed to stand, overnight. The mixture was diluted with water and extracted with light petroleum (B.P. 100-120 C.). The combined extracts were filtered and the solution cooled to 50 C. The solid w-hydroxymethyl longifolene (approx. 195 g.) which then precipitated was then quickly filtered ofi.

EXAMPLE I Perfume with woody base Constituents of perfumery composition: Parts by weight Cedar wood oil (American) 400 Methyl ionone 100 Patchouli oil (Seychelles) 400 Vetiver oil (Bourbon) 100 Such a composition gives the odour effect of a mixture of the individual ingredients with the note of the cedar wood oil predominating. After application to a substrate the notes of different constituents predominate at different times.

The addition of 50 parts of w-hydroxymethyl longifolene had the effect of blending together the mixture and at the same time accentuated the Warm woody note of the Patchouli oil. This character was maintained throughout an extended dry out period.

On the other hand when 50 parts of w-acetoxymethyl longifolene was used instead, it blended the mixture similarly, but resulted in the typical root-like character of the Vetiver Oil as well as the note of the Patchouli Oil being accentuated. Again the total odour characteristics were maintained through an extended dry out period.

EXAMPLE III Perfume of sophisticated aldehyde base Constituents of perfumery composition: Parts by weight Undecylenic aldehyde 20 'y-Nonalactone 10 Methyl nonyl acetaldehyde 10 Hydroxycitronellal 50 Methyl ionone Pacthouli Oil (Seychelles) 50 Sandalwood Oil (East Indian) Vetiveryl acetate 500 It was found that the addition of 50 parts of either w-hydroxymethyl longifolene or w-acetoxymethyl longifolene caused a blending together of the various aldehydic notes which was otherwise achieved only after several months maturation of the composition. This effect was maintained throughout an extended dry out period as also was the overall character of the perfume.

EXAMPLE -III Perfume of simple floral (rose) type Constituents of perfumery composition: Parts by weight 10% solution of undecylenic aldehyde in phenyl ethyl alcohol 5 10% solution of ethylmethylphenyl glycidate Addition of '50 parts of either w-hydroxymethyl longifolene or w-acetoxymethyl longifolene had the effect of blending the above mixture into a composition with a smooth note of roses. At the same time its light fruity top note was accentuated. The fixative effect of the longifolene derivatives caused the composition to maintain its overall character over a long dry out period, whereas when the derivative was omitted the perfumery effect desired from the composition was lost after a short period of exposure on a substrate.

We claim:

1. A compounded erfumery composition containing at least one perfumery ingredient, and in addition to said perfumery ingredient, containing 0.1% to 50% by weight based on the total composition of at least one longifolene derivatives selected from the group consisting of w-hydroxymethyl longifolene and w-acyloxymethyl longifolenes wherein the acyl group has from 2 to 4 carbon atoms whereby said longifolene derivative has a fixing, blending and enhancing elfect on said perfumery composition.

2. A composition according to claim 1 which comprises at least one longifolene derivative selected from the group consisting of w-hydroxymethyl longifolene, and W-acetoxymethyl longifolene.

3. A composition according to claim 1 containing said longifolene derivative or derivatives in a concentration of from 0.1% to 20% by weight based on the total composition.

4. A composition according to claim 3 containing said longifolene derivative or derivatives in a concentration of from 0.1 to percent by weight based on the total composition.

5. A composition according to claim 4 containing said longifolene derivative or derivatives in a concentration of from 3 to 7 percent by weight based on the total composition.

6. A compounded perfumery composition containing an effective amount of at least one perfumery material selected fro-m the group consisting of Patchouli oil, Vetivertype perfumery compounds, ionone perfume compounds, methylionone perfume compounds, n-alkanal and methyl n-alkanal perfume compounds having from 7 to 12 carbon atoms, and perfumery lactones, and containing 0.1% to 50% by weight based on said compounded perfumery composition of at least one longifolene derivative selected from the group consisting of w-hydroxymethyl longifolene and w-acyloxymethyl longifolenes wherein the acyl group has from 2 to 4 carbon atoms whereby said longifolene derivative has a fixative effect on said perfumery composition.

7. A composition according to claim 6 containing said longifolene derivative or derivatives in a concentration of from 0.1% to 20% by weight based on the total composition.

8. A composition according to claim 7 containing said longifolene derivative or derivatives in a concentration of from 0.1 to 10 percent by weight based on the total composition.

9. A composition according to claim 8 containing said longifolene derivative or derivatives in a concentration of from 3 to 7 percent by weight based on the total composition.

10. A composition according to claim 8 wherein said perfumery material is Vetiveryl acetate.

11. A composition according to claim 8 wherein perfumery material is Vetiveryl oil.

12. A composition according to claim 8 wherein perfumery material is Patchouli oil.

13. A composition according to claim 8 wherein erfumery material is Cedar wood oil.

14. A composition according to claim 8 wherein perfumery material is Sandalwood oil.

15. A composition according to claim 8 wherein perfumery material is ionone.

16. A composition according to claim 8 wherein perfumery material is methylionone.

17. A composition according to claim 8 wherein perfumery material is 'y-nonalactone.

18. A composition according to claim 8 wherein perfumery material is citronellyl esters.

19. A composition according to claim 8 wherein perfumery material is geraniol.

20. A composition according to claim 8 wherein perfumery material is phenyl ethyl alcohol.

21. A composition according to claim 8 wherein perfumery material is methyl nonyl acetaldehyde.

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References Cited Chem. Abst. Subject Index, vol. 5665 (1962-1966), p. 131233.

SAM ROSEN, Primary Examiner 

